Tetrameric clusters

A more detailed representation of the reaction requires more intimate knowledge of the enolate structure. Studies of ketone enolates in solution indicate that both tetrameric and dimeric clusters can exist Tetrahydrofliran, a solvent in which many synthetic reactions are performed, favors tetrameric structures for the lithium enolate of isobutyr-ophenone, for example. ... 

The structure and bonding in lithium methyl have been particularly fully studied. The crystal structure consists of interconnected tetrameric units (LiMe)4 as shown in Fig. 4.17 the individual Li4C4 clusters consist of a tetrahedron... 

AgPh is a colourless solid [144] that is rather insoluble in non-donor solvents and appears to be polymeric (AgPh) (n > 10) in addition mixed compounds (AgPh) .AgN03 (n = 2,5) can also be obtained that involve silver clusters. Mesitylsilver is a thermally stable (but light-sensitive) white crystalline solid in the solid state it is tetrameric (in contrast to the pentameric copper and gold analogues) ... 

Fig. 3. The tetrameric structure of the MoFe protein (Kpl) from Klebsiella pneumoniae (7). The two FeMoco clusters and the P clusters are depicted by space-filling models and the polypeptides by ribbons diagrams (MOLSCRIPT (196)). The FeMoco clusters are bound only to the a subunits, whereas the P clusters span the interface of the a and j8 subunits.

The ferredoxins isolated from D. gigas have been quite extensively studied by different experimental approaches and spectroscopic techniques and will be used here as a reference system. Ferredoxin I D. gigas Fdl) and ferredoxin II (D. gigas Fdll) (60-62) are composed of the same polypeptide chain (58 amino acids, 6 cysteines) (63). D. gigas Fdl is a dimer and contains a single [4Fe-4S], whereas the same monomeric unit of the tetrameric D. gigas Fdll contains a single [3Fe-4S] ° cluster. 

Cs2Ti4Nb6Clis06. (c) A tetrameric propellerlike (Ti4CI]206) unit in Cs2Ti4Nb6Chg06 built from four (TiLj) octahedra that share edges, (d) Cluster unit in PbLusNbeChsOe. 

Archibald, S.J., Alcock, N.W., Busch, D.H. and Whitcomb, D.R. (2000) Synthesis and characterization of silver(I) complexes with C-AIkyl functionahzed N,f/-Diphenylamidrnates Tetrameric and trrmeric structural motifs. Journal of Cluster Science, 11, 261—283. 

In view of this, it is not surprising that dithiocarbamato compounds with copper in the oxidation state + 3 are stable instead it must be regarded as unexpected that Cu(I) dithiocarbamato complexes exist. The latter complexes are not simply monomeric, but they are tetrameric metal cluster compounds. Obviously, the stability must be attributed to the metal-metal bond rather than to the stabilising effect of the ligand. 

The crystal structures of many organolithium compounds have been determined.44 Phenyllithium has been crystallized as an ether solvate. The structure is tetrameric with lithium and carbon atoms at alternating corners of a highly distorted cube. The lithium atoms form a tetrahedron and the carbons are associated with the faces of the tetrahedron. Each carbon is 2.33 A from the three neighboring lithium atoms and an ether molecule is coordinated to each lithium atom. Figures 7.2a and b show, respectively, the Li-C cluster and the complete array of atoms, except for hydrogen 45 Section 6.2 of Part A provides additional information on the structure of organolithium compounds. 

Fig. 7.2. Crystal structure of tetrameric phenyllithium diethyl etherate (a) tetrameric C4Li4 cluster (b) complete structure except for hydrogens. Reproduced from J. Am. Chem. Soc.,...

Fig. 6. Two partial views of the structure [C6H4CH2NMe2]2Si(OLi)(OH) 4-2LiC12CHCl3. (a) The immediate environment around each Si. (b) A representation of the tetrameric core of the cluster (aromatic substituents omitted for clarity). 

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